Hydrotreating of hydrocarbons

ABSTRACT

A PROCESS FOR HYDROCARBONS AND MIXTURES OF HYDROCARBONS UTILIZING A CATALYSTIC COMPOSITE OF A POROUS CARRIER MATERIAL , A GROUP VIII NOBLE METAL COMPONENT AND A GERMANIUM COMPONENT. APPLICABLE TO CHARGE STOCKS CONTAINING SULFUROUS COMPOUNDS AND AROMATIC HYDROCARBONS, HE HYDROTREATING CONDITIONS CAN BE CONTROLLED TO EFFECT A PARTICULAR END RESULT INCLUDING THE RING-OPENING OF CYCLIC HYDROCARBONS, DESULFURIZATION, DENITRIFICATION, SELECTIVE OLEFIN SATURATION, ETC.

United States Patent 3,736,252 HYDROTREATING 0F HY DROCARBQNS John C. Hayes, Palatine, Ill., assignor to Universal Oil Products Company, Des Plaines, Ill.

No Drawing. Application July 7, 1969, Ser. No. 839,643, now Patent No. 3,607,727, dated Sept. 21, 1971, which is a continuafion-in-part of application Ser. No. 828,762, May 28, 1969, now Patent No. 3,578,584, dated May 11, 1971. Divided and this application Aug. 17, 1970, Ser. No. 64,643

Int. Cl. Cg 23/02 US. Cl. 208255 3 Claims ABSTRACT OF THE DISCLOSURE A process for hydrotreating hydrocarbons and mixtures of hydrocarbons utilizing a catalytic composite of a porous carrier material, a Group VIII noble metal component and a germanium component. Applicable to charge stocks containing sulfurous compounds and aromatic hydrocarbons, the hydrotreating conditions can be controlled to effect a particular end result including the ring-opening of cyclic hydrocarbons, desulfurization, denitrification, selective olefin saturation, etc.

RELATED APPLICATIONS The present invention encompasses the use of a catalytic composite of a porous carrier material, a Group VIII noble metal component and a germanium component in the hydrotreating of hydrocarbons and mixtures of hydrocarbons. As utilized herein, the term hydrotreating is intended to be synonymous with the term hydroprocessing, and involves the conversion of hydrocarbons at operating conditions selected to effect a chemical consumption of hydrogen. Included Within the processes intended to be encompassed by the term hydrotreating are ring-opening of cyclic hydrocarbons, hydrorefining (for nitrogen removal and olefin saturation), desulfurization (often included in hydrorefining) and hydrogenation, etc. In essence, therefore, the present invention is directed toward the removal of various contaminating influences from a variety of hydrocarbonaceous charge stocks. As will be recognized, one common attribute of these processes, and the reactions being effected therein, is that they are all hydrogen-consuming, and are, therefore, exothermic in nature.

The individual characteristics of the foregoing hydrotreating processes, including preferred operating conditions and techniques, will be hereinafter described in greater detail. The subject of the present invention is the use of a catalytic composite which has exceptional activity and resistance to deactivation when employed in a hydrogen-consuming process. Such processes require a catalyst having both a hydrogenation function and a cracking function. More specifically, the present process uses a dual-function catalytic composite which enables substantial improvements in those hydrotreating processes that have traditionally used a dual-function catalyst. The catalytic composite constitutes a porous carrier material, a Group VIII noble metal component and a germanium component for improved activity, product selectivity and operational stability characteristics.

Catalytic composites are used to promote hydrocarbon conversion reactions such as hydrocracking, isomerization, dehydrogenation, hydrogenation, desulfurization, reforming, ring-opening, cyclization, aromatization, alkylation and transalkylation, polymerization, cracking, etc., some of which reactions are hydrogen-producing while others are hydrogen-consuming. In using the term hydrogen-consuming, I intend to exclude those processes wherein the principal hydrogen consumption involves the saturation of light olefins, resulting fom undesirable cracking, which produces the light paratfins, methane, ethane and propane. It is to the latter group of reactions, hydrogen-consuming, that the present invention is applicable. In many instances, the commercial application of these catalysts is in processes where more than one of these reactions proceed simultaneously. An example of this type of process would be the conversion of aromatic hydrocarbons into jet fuel components, principally straight, or slightly branched paraflins, wherein both ring opening and hydrogenation are effected.

Regardless of the reaction involved, or the particular process, it is very important that the catalyst exhibit not only the capability to perform its specified functions initially, but also perform them satisfactorily for prolonged period of time. The analytical terms employed in the art to measure how efiicient a particular catalyst performs its intended functions in a particular hydrocarbon conversion process, are activity, selectivity and stability. For the purpose of discussion, these terms are conveniently defined herein, for a given charge stock, as follows:

(1) Activity is a measure of the ability of the catalyst to convert a hydrocarbon feed stock into products at a specified severity level, where severity level alludes to the operating conditions employed-the temperature, pres sure, liquid hourly space velocity and hydrogen concentration;

(2) Selectivity refers to the weight percent or volume percent of the reactants that are converted into the desired product and/ or products;

(3) Stability connotes the rate of change of the activity and selectivity parameters with timeobviously, the smaller rate implying the more stable catalyst.

With respect to a hydrogen-consuming process, for example desulfurization, activity, stability and selectivity are similarly defined. Thus, activity connotes the quantity of sulfurous compounds converted into hydrogen sulfied and hydrocarbons. Selectivity refers to the quantity of charge stock which has been cracked to produce light, normally gaseous paraflins. Stability connotes the rate of change of activity and selectivity.

As is well known to thos skilled in the art, the principal cause of observed deactivation or instability of a dualfunction catalyst is associated with the fact that coke forms on the surface of the catalyst during the course of the reaction. More specifically, in the various hydrocarbon conversion processes, and especially those which are categorized as hydrogen-consuming, the operating conditions utilized result in the formation of high molecular weight, black, solid or semi-solid, hydrogen-poor carbonaceous material which coats the surface of the catalyst and reduces its activity by shielding its active sites from the reactants. Accordingly, a major problem facing Workers in this area is the development of more active and selective catalytic composites that are not as sensitive to the presence of these carbonaceous materials and/ or have the capability to suppress the rate of formation of these materials at the operating conditions employed in a particular process.

I have now found a dual-function catalytic composite which possesses improved activity, selectivity and stability when employed in the hydrotreating of hydrocarbons, wherein there is effected a chemical consumption of hydrogen. In particular, I have found that the use of a catalytic composite of a Group VIII noble metal component and a germanium component with a porous carrier material improves the overall operation of these hydrogen-consuming processes. The present invention essentially involves the use of a catalyst in which a germanium component has been added to a dual-function conversion catalyst, and enables the performance characteristics of the process to be sharply and materially improved. An essential condition associated with the acquisition of this improved performance is the oxidation state of the germanium component utilized in this catalyst. As a result of my investigations, I have determined that the germanium component must be utilized in a positive oxidation state (i.e., either +2 or +4) and that germanium component must be uniformly distributed throughout the porous carrier material. In short, the present invention essentially involve the finding that the addition of a controlled amount of a germanium component, in a positive oxidation state, to a dual-function hydrocarbon conversion catalyst containing a Group VIII noble metal component enables performance characteristics of the catalyst to be sharply and materally improved when used in a hydrogen-consuming process.

OBJECTS AND EMBODIMENTS An object of the present invention is to afford a process for the hydrotreating of a hydrocarbon, or mixtures of hydrocarbons. A corollary objective is to improve the selectivity and stability of hydrotreating utilizing a. highly active, germanium component-containing catalytic composite.

A specific object of my invention resides in the improvement of hydrogen-consuming processes including hydro-refining, ring-opening for jet fuel production, bydrogenation, desulfurization, denitrification, etc. Therefore, in one embodiment, the present invention encorn passes a process for hydrotreating a hydrocarbonaceous charge stock containing sulfurous compounds and aromatic hydrocarbons which comprises reacting said charge stock and hydrogen in a reaction zone and in contact with a catalytic composite of a Group VIII noble metal component, a germanium component combined with a porous carrier material.

In another embodiment, the process is further characterized in that the catalytic composite is reduced and sulfided prior to contacting the hydrocarbon feed stream. In still another embodiment, my invention involves a process for hydrogenating a coke-forming hydrocarbon distillate containing di-olefinic and mono-olefinic hydrocarbons, and aromatics, which process comprises reacting said distillate with hydrogen, at a temperature below about 500 F., in contact with a catalytic composite of an alumina-containing refractory inorganic oxide, a Group VIII noble metal component, an alkalinous metal component and a germanium component, and recovering an aromatic/mono-olefinic hydrocarbon concentrate substantial- 1y free from conjugated di-olefinic hydrocarbons.

Other objects and embodiments of my invention relate to additional details regarding preferred catalytic ingredients, the concentration of components in the catalytic composite, methods of catalyst preparation, individual operating conditions for use in the various hydrotreating processes, preferred processing techniques and the like particulars which are hereinafter given in the following, more detailed summary of my invention.

SUMMARY OF INVENTION As hereinabove set forth, the present invention involves the hydrotreating of hydrocarbons and mixtures of hydrocarbons, for hydrogenation and/or contaminant removal, utilizing a particular catalytic composite. This catalyst comprises a porous carrier material having combined therewith a Group VIII noble metal component and a germanium component; in many applications, the catalyst will also contain a halogen component, and in some select applications, an alkali metal or alkaline-earth metal component. Considering first the porous carrier material, it is preferred that it be a porous, adsorptive, high-surface area support having a surface area of about 25 to about 5 00 square meters per gram. It is intended to include carrier materials which have traditionally been utilized in dual-function hydrocarbon conversion catalysts. In particular, suitable carrier materials are selected from the group of amorphous refractory inorganic oxides including alumina, titania, zirconia, chromia, magnesia, thoria, boria, silica-alumina, silica-magnesia, chromia-alumina, alumina-boria, alumina-silica-boron phosphate, silicazirconia, etc. When of the amorphous type, the preferred carrier material is either a composite of alumina and silica, with silica being present in an amount of about 10.0% to about 90.0% by weight, or alumina in and of itself.

In many hydroprocessing applications of the present invention, the carrier material will constitute a crystalline aluminosilicate, often referred to as being zeolitic in nature. This may be naturally-occurring, or synthetically prepared, and includes mordenite, faujasite, Type A or Type U molecular sieves, etc. When utilized as the carrier material, the zeolitic material may be in the hydrogen form, or in a form which has been treated with multivalent cations.

As hereinabove set forth, the porous carrier material, for use in the process of the present invention, is a refractory inorganic oxide, either alumina in and of itself, or in combination with one or more other refractory inorganic oxides, and particularly in combination with silica. When utilized as the sole component of the carrier material, the alumina may be of the =gamma-, eta-, or thetaalumina type, with gamma-, or eta-alumina giving the best results. In addition, the preferred carrier materials have an apparent bulk density of about 0.30 to about 0.70 gm./cc. and surface area characteristics such that the average pore diameter is about 20 to about 300 Angstroms, the pore volume is about 0.10 to about 1.0 milliliters per gram and the surface area is about to about 500 square meters per gram. Whatever type of refractory inorganic oxide is employed, it may be activated prior to use by one or more treatments including drying, calcination, steaming, etc. For example, the alumina carrier may be prepared by adding a suitable alkaline reagent, such as ammonium hyroxide, to a salt of aluminum, such as alumrnum chloride, aluminum nitrate, etc., in an amount to form an aluminum hydroxide gel which, upon drying and calcination, is converted to alumina. The carrier material may be formed in any desired shape such as spheres, pills, cakes, extrudates, powders, granules, etc., and may further be utilized in any desired size.

When a crystalline aluminosilicate, or zeolitic material, is intended for use as the carrier, it may be prepared in a number of ways. One common way is to mix solutions of sodium silicate, or colloidal silica, and sodium aluminate, and allow these solutions to react to form a. solid crystalline aluminosilicate. Another method is to contact a solid inorganic oxide, from the group of silica, alumina, and mixtures thereof, with an aqueous treating solution containing alkali metal cations (preferably sodium) and anions selected from the group of hydroxyl, silicate and alurninate, and allow the solid-liquid mixture to react until the desired crystalline aluminosilicate has been formed. One particular method is especially preferred when the carrier material is intended to be a crystalline aluminosilicate. This stems from the fact that the method can produce a carrier material of substantially pure crystalline aluminosilicate particles. In employing the term substantially pure, the intended connotation is an aggregate particle at least 90.0% by weight of which is zeolitic. Thus, this carrier is distinguished from an amorphous carrier material, or prior art pills and/ or extrudates in which the zeolitic material might be dispersed within an amorphous matrix with the result that only about 40.0% to about 70.0% by weight of the :final particle is zeolitic. The preferred method of preparing the carrier material produces crystalline aluminosilicates of the faujasite modification, and utilizes aqueous solutions of colloidal silica and sodium aluminate.

One essential constituent of the composite for use in the present invention is a germanium component, and it is an essential feature that the germanium component is present in the composite in an oxidation state above that of the elemental metal. That is to say, the germanium component necessarily exists within the catalytic composite in either the +2 or +4 oxidation state, the latter being the most likely state. Accordingly, the germanium component will be present in the composite as a chemical compound, such as the oxide, sulfide, halide, etc., wherein the germanium is in the required oxidation state, or in a chemical combination with the carrier material, in which combination the germanium exists in this higher oxidation state. On the basis of the evidence currently available, it is believed that the germanium component in the subject composite exists as germanous or germanic oxide. It is important to note that this limitation on the state of the germanium component requires extreme care in the preparation and use of the subject composite in order to insure that it is not subjected to high temperature reduction conditions (reduction at temperatures above 1000 F.) which are effective to produce the germanium metal. This germanium component may be incorporated in the catalytic composite in any suitable manner known to the art such as by co-precipitation or cogellation with the porous carrier material, ion-exchange with the gelled carrier material, or impregnation with the carrier material either after, or before it is dried and calcined. It is to be noted that it is intended to include within the scope of the present invention all conventional methods for incorporating a metallic component in a catalytic composite and the particular method of incorporation used is not deemed to be an essential feature of the present invention. One method of incorporating the germanium component into the catalytic composite involves co-precipitating the germanium component during the preparation of the carrier material. This method typically involves the addition of a suitable soluble germanium compound such as germanium tetrachloride to the inorganic oxide hydrosol and then combining the hydrosol with a suitable gelling agent and dropping the resultant mixture into an oil bath maintained at elevated temperatures. The droplets remain in the oil bath until they set and form hydrogel spheres. The spheres are withdrawn from the oil bath and subjected to specific aging treatments in oil and in an ammoniacal solution. The aged spheres are washed and dried at a temperature of about 200 F. to 400 F and thereafter calcinated at an elevated temperature of about 850 F. to about 1300 F. Further details of spherical particle production may be found in United States Pat. 2,620,- 314, issued to James Hoekstra. After drying and calcining the resulting gelled carrier material there is obtained an intimate combination of alumina and germanium oxide. A preferred method of incorporating the germanium component into the catalytic composite involves utilization of a soluble, decomposable compound of germanium to impregnate the porous carrier material. In general, the solvent used in this impregnation step is selected on the basis of the capability to dissolve the desired germanium compound and is preferably an aqueous, or alcoholic solution. Thus, the germanium component may be added to the carrier material by commingling the latter with a solution of a suitable germanium salt or suitable compound of germanium such as germanium tetrachloride, germanium difluoride, germanium tetrafluoride, germanium di-iodide, germanium monosulfide, and the like compounds. In general, the germanium component can be impregnated either prior to, simultaneously with, or after the Group VIII noble metal component. However, I have found that excellent results are obtained when the germanium component is impregnated simultaneously with the Group VIII noble metal component. In fact, I have determined that a preferred impregnation solution contains chloroplatinic acid, hydrogen chloride, and germanous oxide dissolved in chlorine water, especially when the catalyst is intended to contain combined chlorine. Following the impregnation step, the resulting composite is dried and calcined as explained hereinafter.

Regardless of which germanium compound is used in the preferred impregnation step, it is important that the germanium component be uniformly distributed throughout the carrier material. It is preferred to use a volume ratio of impregnation solution to carrier material of at least 1.5 :1 and preferably about 2:1 to about 10:1, or more. Similarly, it is preferred to use a relatively long contact time during the impregnation step ranging from about 4 hour up to about /2 hour, or more, before drying to remove excess solvent in order to insure a high dispersion of the germanium component on the carrier material. The carrier material is, likewise, preferably constantly agitated during this preferred impregnation step.

As previously indicated, the catalyst for use in the process of the present invention also contains a Group VIII noble metal component. Although the process of the present invention is specifically directed to the use of a catalytic composite containing platinum, it is intended to include other Group VIII noble metals such as palladium, rhodium, ruthenium, osmium and iridium. The Group VIII noble metal component, for example platinum, may exist within the final catalytic composite as a compound such as an oxide, sulfide, halide, etc., or in an elemental state. The Group VIII noble metal component generally comprises about 0.01% to about 2.0% by weight of the final composite, calculated on an elemental basis. Excellent results are obtained when the catalyst contains about 0.3% to about 0.9% by weight of the Group VIII noble metal. In addition to platinum, another particularly preferred Group VIII noble metal component is palladium, or a compound of palladium.

The Group VIII noble metal component may be incorporated within the catalytic composite in any suitable manner including co-precipitation or cogellation with the carrier material, ion-exchange, or impregnation. A preferred method of preparation involves the utilization of a water-soluble compound of a Group VIII noble metal component in an impregnation technique. Thus, a platinum component may be added to the carrier material by commingling the latter with an aqueous solution of chloroplatinic acid. Other water-soluble compounds of platinum may be employed, and include ammonium chloroplatinate, platinum chloride, dinitro diamino platinum, etc. The use of a platinum chloride compound, such as chloroplatinic acid, is preferred since it facilitates the incorporation of both the platinum component and at least a minor quantity of the halogen component in a single step. In addition, it is generally preferred to impregnate the carrier material after it has been calcined in order to minimize the risk of washing away the valuable Group VIII noble metal compounds; however, in some instances it may prove advantageous to impregnate the carrier material when it exists in a gelled state. Following impregnation, the composite will generally be dried at a temperature of about 200 F. to about 400 F., for a period of from 2 to about 24 hours, or more, and finally calcined at a temperature of about 700 F. to 1100 F., in an atmosphere of air, for a period of about 0.5 to about 10 hours.

Although not essential to successful hydroprocessing in all cases, in fact detrimental in some, a halogen component may be incorporated into the catalytic composite.

Accordingly, a catalytic composite, suitable for use in at least one embodiment of the present process, comprises a combination of a Group VIII noble metal component, a germanium component and a halogen component. Although the precise form of the chemistry of the association of the halogen component with the carrier material and metallic components is not accurately known, it is customary in the art to refer to the halogen component as being combined with the carrier material, or with the other ingredients of the catalyst. The combined halogen may be either fluorine, chlorine, iodine, bromine, or mixtures thereof. Of these, fluorine and particularly chlorine are preferred for the hydrocarbon hydrotreating processes encompassed by the present invention. The halogen may be added to the carrier material in any suitable manner, and either during preparation of the carrier, or before, or after the addition of the other components. For example, the halogen may be added at any stage in the preparation of the carrier material, or to the calcined carrier material, as an aqueous solution of an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc. The halogen component or a portion thereof may be composited with the carrier material during the impregnation of the latter with the Group VIII noble metal component. The inorganic oxide hydrosol, which is typically utilized to form an amorphous carrier material, may contain halogen and thus contribute at least a portion of the halogen component to the final composite. The quantity of halogen is such that the final catalytic composite contains about 0.1% to about 1.5% by weight, and preferably from about 0.5% to about 1.2% calculated on an elemental basis.

With respect to the quantity of the germanium component, it is preferably about 0.01% to about 5.0% by weight, calculated on an elemental basis. Regardless of the absolute quantities of the germanium component and the platinum group component, the atomic ratio of the Group VIII noble metal to the germanium contained in the catalyst is preferably selected from the range of about 0.1:1 to about 3:1, with excellent results being achieved at an atomic ratio of about 0.5 :1 to about 1.5 :1. This has been found to be particularly true when the total content of the germanium component plus the Group VIII noble metal component is fixed in the range of about 0.15 to about 3.0% by Weight. Accordingly, examples of suitable catalytic composites, considering only the Group VIII noble metal component and the germanium component are as follows:

0.5% by Weight of germanium, 0.75 by weight of platinum;

0.1% by weight of germanium, 0.65% by weight of platinum;

0.375% by weight of germanium, 0.375% by weight of platinum;

1.0% by weight of germanium, 0.5% by weight of platinum;

0.25% by Weight of germanium, 0.5% by weight of platinum;

0.75% by weight of palladium, 0.5% by Weight of germanium;

0.65 by weight of palladium, 0.1% by weight of germanium;

0.375% by weight of palladium, 0.375% by weight of germanium;

0.5% by weight of palladium, 1.0% by Weight of germanium; and,

0.5% by Weight of palladium, 0.25% by weight of germanium.

When used in many of the hydrogen-consuming processes hereinbefore described, the foregoing quantities of metallic components will be combined with a carrier material of alumina and silica, wherein the silica concentration is 10.0% to about 90.0% by weight. In those processes wherein the acid function of the catalytic composite must necessarily be attenuated, the metallic components will be combined with a carrier material consisting essentially of alumina. In the latter situation, a halogen component is not combined with the catalytic composite, and, the inherent acid function of Group VIII noble metals is further attenuated through the addition of from 0.01% to about 1.5% by weight of an alkalinous metal component.

One such process, in which the acid function of the catalyst employed must necessarily be attenuated, is the process wherein an aromatic hydrocarbon/olefinic hydrocarbon mixture is subjected to hydrogenation to produce a product stream substantially free from conjugated diolefinic hydrocarbons and rich in aromatics. In order to avoid ring-opening which results in loss of the desired aromatic hydrocarbons, and to inhibit polymer formation, an alkalinous metal component is combined with the cat alytic composite in an amount of from 0.01% to about 1.5% by weight. This component is selected from the group of lithium, sodium, potassium, rubidium, cesium, barium, strontium, calcium, magnesium, beryllium, mixtures of two or more, etc. In general, more advantageous results are achieved through the use of the alkali metal, particularly lithium and/or potassium.

In those instances where a halogen component is utilized in the catalyst, it has been determined that more advantageous results are obtained when the halogen content of the catalyst is adjusted during the calcination step through the inclusion of a halogen, or a halogen-containing compound in the air atmosphere. In particular, when the halogen component of the catalyst is chlorine, for example, it is preferred to use a mole ratio of Water to hydrochloric acid of about 20:1 to about :1 during at least a portion of the calcination step in order to adjust the final chlorine content of the composite toa range of about 0.5% to about 1.2% by weight.

Prior to its use, the resultant calcined catalytic composite may be subjected to a substantially Water-free reduction technique. This technique is designed to insure a uniform and finely-divided dispersion of the metallic components throughout the carrier material. Preferably, substantially pure and dry hydrogen (i.e., less than about 30.0 vol. ppm. of water) is employed as the reducing agent. The calcined catalyst is contacted at a temperature of about 800 F. to about 1000 F., and for a period of time of about 0.5 to about 2 hours, in order to minimize the risk of reducing the germanium component, but effected to substantially reduce the Group VIII noble metal component. This reduction technique may be performed in situ as part of a start-up sequence provided precau tions are observed to pre-dry the unit to a substantially water-free state.

Again, with respect to effecting hydrogen-consuming reactions, the process may be improved when the reduced composite is subjected to a presulfiding operation designed to incorporate from about 0.05 to about 0.50% by weight of sulfur, on an elemental basis, in the catalytic composite. This presulfiding treatment takes place in the presence of hydrogen and a suitable sulfur-containing compound including hydrogen sulfide, lower molecular weight mercaptans, organic sulfides, etc. The procedure constitutes treating the reduced catalyst with a sulfiding gas, such as a mixture of hydrogen and hydrogen sulfide having about 10 moles of hydrogen per mole of hydrogen sulfide, and at conditions sufficient to effect the desired incorporation of sulfur. These conditions include a temperature ranging from about 50 F. up to about 1000 F.

According to the present invention, the hydrocarbon charge stock and hydrogen are contacted with a catalyst of the type described above in a hydrocarbon conversion, or reaction zone. The particular catalyst employed is dependent upon the characteristics of the charge stock as well as the desired end result. The contacting may be ac complished by using the catalyst in a fixed-bed system, a

moving-bed system, a fluidized-bed system, or in a batchtype operation; however, in view of the risk of attrition losses of the valuable catalyst, it is preferred to use the fixed-bed system. Furthermore, it is well known that a fixed-bed catalytic system offers many operational advantages. In this type of system, a hydrogen-rich gas and the charge stock are preheated by any suitable heating means to the desired temperature, and then are passed into a conversion zone containing the fixed-bed of the catalytic composite. It is understood, of course, that the conversion zone may be one or more separate reactors having suitable means therebetween to insure that the desired conversion temperature is maintained at the entrance to each reactor. It is also to be noted that the reactants may be contacted with the catalyst bed in either upward, downward, or radial flow fashion, with the latter being preferred. Additionally, the reactants may be in the liquid phase, a mixed liquid-vapor phase, or a vapor phase when they contact the catalyst.

The operating conditions imposed upon the reaction zones are dependent upon the particular hydrotreating process being effected. However, these operating conditions will include a pressure from about 400 to about 5,000 p.s.i.g., a liquid hourly space velocity of about 0.1 to about 10.0, and a hydrogen concentration within the range of about 1,000 to about 50,000 standard cubic feet per barrel. In view of the fact that the reactions being effected are exothermic in nature, an increasing temperature gradient is experienced as the hydrogen and feed stock traverses the catalyst bed. For any given process, it is desirable to maintain the maximum catalyst bed temperature below about 900 R, which temperature is virtually identical to that conveniently measured at the outlet of the reaction zone. Hydrogen-consuming processes are conducted at a temperature in the range of about 200 F. to about 900 F., and it is intended herein that the stated temperature of operation alludes to the maximum catalyst bed temperature. In order to assure that the catalyst bed temperature does not exceed the maximum allowed for a given process, the use of conventional quench streams, either normally liquid or gaseous, introduced at one or more intermediate loci of the catalyst bed, may be utilized. In some of the hydrotreating processes encompassed by the present invention, a portion of the normally liquid product efiluent will be recycled to combine with the fresh hydrocarbon charge stock. In these situations, the combined liquid feed ratio (defined as volumes of total liquid charge to the reaction zone per volume of fresh feed charge to the reaction zone) will be within the range of about 1.1 to about 6.0.

Specific operating conditions, processing techniques, particular catalytic composites and other individual process details will be given in the following detailed description of several of the hydrotreating processes to which the present invention is applicable. These will be presented by way of examples given in conjunction with commercially-scaled operating units. In presenting these examples, it is not intended that the invention be limited to the specific illustrations, nor is it intended that a given process be limited to the particular operating conditions, catalytic composite, processing techniques, charge stock, etc. It is understood, therefore, that the present invention is merely illustrated by the specifics hereinafter set forth.

EXAMPLE I One hydrocarbon hydroprocessing scheme, to which the present invention is applicable, involves the hydrorefining of coke-forming, naphtha boiling range hydrocarbon distillates. These hydrocarbon distillates are generally sulfurous in nature, and contain mono-olefinic, di-olefinic and aromatic hydrocarbons. Through the utilization of a catalytic composite comprising both a germanium component and a Group VIII noble metal component, increased selectivity and stability of operation is obtained; selectivity is most noticeable with respect to the retention of aromatics, and in hydrogenating conjugated di-olefinic and mono-olefinic hydrocarbons. 'Such charge stocks generally result from diverse conversion processes including the catalytic and/ or thermal cracking of petroleum, sometimes referred to as pyrolysis, the destructive distillation of wood or coal, shale oil retorting, etc. The impurities in these distillate fractions must necessarily be removed before the distillates are suitable for their intended use, or which when removed, enhance the value of the distillate fraction for further processing. Frequently, it is intended that these charge stocks be substantially desulfurized and saturated to the extent necessary to remove the conjugated diolefins, while simultaneously retaining the aromatic hydrocarbons. When subjected to hydrorefining for the purpose of removing the contaminating influences, there is encountered difliculty in effecting the desired degree of reaction due to the formation of coke and other carbonaceous material.

As utilized herein, hydrogenating is intended to be synonymous with hydrorefining. The purpose is to provide a highly selective and stable process for hydrogenating coke-forming hydrocarbon distillates, and this is accomplished through the use of a fixed-bed catalytic reaction system utilizing a catalyst comprising a germanium component and a Group VHI noble metal component. There exist two separate, desirable routes for the treatment of coke-forming distillates, for example a pyrolysis naphtha byproduct. One such route is directed toward a product suitable for use in certain gasoline blending. With this as the desired object, the process can be eifected in a single stage, or reaction zone, with the catalytic composite hereinafter specifically described as the first-stage catalyst. The attainable selectivity in this instance resides primarily in the hydrogenation of highly reactive double bonds. In the case of conjugated di-olefins, the selectivity aiforded restricts the hydrogenation to produce mono-olefins, and, with respect to the styrenes, for example, the hydogenation is inhibited to produce alkyl benzenes without ring saturation. The selectivity is accomplished with a minimum of polymer formation either to gums, or lower molecular weight polymers which would necessitate a rerunning of the product before blending to gasoline would be feasible.

Other advantages of restricting the hydrogenating of the conjugated di-olefins and styrenes include: lower hydrogen consumption, lower heat of reaction and a higher octane rating gasoline boiling range product effluent. Also, the non-conjugated di-olefins, such as 1,5 normal hexadiene are not unusually offensive in suitably inhibited gasolines in some locales, and will not react in this first stage. Some fresh charge stocks are sufficiently low in mercaptan sulfur content that direct gasoline blending may be considered, although a mild treatment for mercaptan sulfur removal might be necessary. The considerations are generally applicable to foreign markets, particularly European, where olefinic and sulfurcontaining gasolines are not too objectionable. It must be noted that the sulfurous compounds, and the monoolefins, wherein virgin, or products of di-olefin partial saturation, are unchanged in the single, or first-stage reaction zone. Where however, the desired end result is aromatic [hydrocarbon retention, intended for subsequent extraction, the two-stage route is required. The monoolefins must be substantially saturated in the second stage to facilitate aromatic extraction by way of currently utilized methods. Thus, the desired necessary hydrogenation involves saturation of the mono-olefins, as well as sulfur removal, the latter required for an acceptable ultimate aromatic product. Attendant upon this is the necessity to avoid even partial saturation, or ring-opening of aromatic nuclei.

With respect to one catalytic composite, its principal function involves the selective hydrogenation of conjugated di-olefinic hydrocarbons to mono-olefinic hydrocarbons. This particular catalytic composite possesses unusual stability notwithstanding the presence of relatively large quantities of sulfurours compounds in the fresh charge stock. The catalytic composite comprises an alumina-containing refractory inorganic oxide, a germanium component, a Group VIII noble metal component and an alkalinous component, the latter being preferably potassium and/or lithium. It is especially preferred, for use in this particular hydrocarbon hydroprocessing scheme, that the catalytic composite be substantially free from any acid-acting propensities. The catalytic composite, utilized in the second reaction zone for the primary purpose of etfecting the destructive conversion of sulfurous compounds into hydrogen sulfide and hydrocarbons, is a composite of an alumina-containing refractory inorganic oxide, a Group VIII noble metal component and a germanium component. Through the utilization of a particular sequence of processing steps, and the use of the foregoing described catalytic composites, the formation of high molecular weight polymers and co-polymers is inhibited to a degree which permits processing for an extended period of time. Briefly, this is accomplished by initiating the hydrorefining reactions at temperatures below about 500 F., at which temperatures the coke-forming reactions are not promoted. The operating conditions within the second reaction zone are such that the sulfurous compounds are removed without incurring the detrimental polymerization reactions otherwise resulting were it not for the saturation of the conjugated di-olefiinc hydrocarbons within the first reaction zone.

The hydrocarbon distillate charge stock, for example a light naphtha by-product from a commercial cracking unit designed and operated for the production of ethylene, having a gravity of about 340 APE, a bromine number of about 35.0, a diene value of about 17.5 and containing about 1,600 p.p.m. by weight of sulfur and 75.9 vol. percent aromatic hydrocarbons, is admixed with recycled hydrogen. This light naphtha co-product has an initial boiling point of about 164 F. and an end boiling point of about 333 F. The hydrogen concentration is within the range of from about 1,000 to about 10,000 s.c.f./bbl., and preferably in the narrower range of from 1,500 to about 6,000 s.c.f./bbl. The charge stock is heated to a temperature such that the maximum catalyst temperature is in the range of from about 200 F. to about 500 F., by Way of heat-exchange with various product effluent streams, and is introduced into the first reaction zone at an Ll-ISV in the range of about 0.5 to about 10.0. The reaction zone is maintained at a pressure of from 400 to about 1,000 p.s.i.g., and preferably at a level in the range of from 500 p.s.i.g. to about 900 p.s.i.g.

The temperature of the product effluent from the first reaction zone is increased to a level above about 500 F., and preferably to result in a maximum catalyst temperature in the range of 600 F. to 900 F. When the process is functioning efiiciently, the diene value of the liquid charge entering the second catalytic reaction zone is less than about 1.0 and often less than about 0.3. The conversion of nitrogenous and sulfurous compounds, and the saturation of mono-olefins, contained within the first zone efiiuent, is efiected in the second zone. The second catalytic reaction zone is maintained under an imposed pressure of from about 400 to about 4,000 p.s.i.g., and preferably at a level of from about 500 to about 900 p.s.i.g. The two-stage process is facilitated when the focal point for pressure control is the high pressure separator serving to separate the product effluent from the second catalytic reaction zone. It will, therefore, be maintained at a pressure slightly less than the first catalytic reaction zone, as a result of fluid flow through the sysem. The LHSV through the second reaction zone is about 0.5 to about 10.0, based upon fresh feed only. The hydrogen concentration will be in the range of from 1,000 to about 10,000 s.c.f./-bbl., and preferably from about 1,000 to about 8,000 s.c.f./bbl. Series-flow through the entire system is facilitated when the recycle hydrogen is admixed with the fresh hydrocarbon charge stock. Make-up hydrogen, to supplant that consumed in the overall process, may be introduced from any suitable external source, but is preferably introduced into the system by Way of the efiluent line from the first catalytic reaction zone to the second catalytic reaction zone.

With respect to the naphtha boiling range portion of the product effluent, the sulfur concentration is about 0.1 p.p.m., the aromatic concentration is about 75.1% by volume, the bromine number is less than about 0.3 and the diene value is essentialy nil.

With charge stocks having exceedingly high diene values, a recycle diluent is employed in order to prevent an excessive temperature rise in the reaction system.

Where so utilized, the source of the diluent is preferably a portion of the normally liquid product effluent from the second catalytic reaction zone. The precise quantity of recycle material varies from feed stock to feed stock; however, the rate at any given time is controlled by monitoring the diene value of the combined liquid feed to the first reaction zone. As the diene value exceeds a level of about 25.0, the quantity of recycle is increased, thereby increasing the combined liquid feed ratio; when the diene value approaches a level of about 20.0, or less, the quantity of recycle diluent may be lessened, thereby decreasing the combined liquid feed ratio.

With another so-called pyrolysis gasoline, having a gravity of about 36.4 API, containing 600 p.p.m. by weight of sulfur, 78.5% by volume of aromatics, and having a bromine number of 45 and a diene value of 25.5 it is initially processed in a first reaction zone containing a catalytic composite of alumina, 0.5% by weight of lithium, 0.20% by weight of palladium and 0.375% by weight of germanium, calculated as the elements. The fresh feed charge rate is 3,300 bbl./day, and this is admixed with 2,475 bbl./day of the normally liquid diluent. Based upon fresh feed only, the LHSV is 2.5 and the hydrogen circulation rate is 1,750 s.c.f./bbl. The charge is raised to a temperature of about 250 F., and enters the first reaction zone at a pressure of about 840 p.s.i.g. The product effiuent emanates from the first reaction zone at a pressure of about 830 p.s.i.g. and a temperature of about 350 F. The effluent is admixed with about 660 s.c.f./bbl. of make-up hydrogen, and the temperature is increased to a level of about 545 F., the heated stream is introduced into the second reaction zone under a pressure of about 790 p.s.i.g. The LHSV, exclusive of the recycle diluent, is 2.5, and the hydrogen circulation rate is about 1,500. The second reaction zone contains a catalyst of a composite of alumina, 0.375% by weight of platinum and 0.25% by weight of germanium. The reaction product eiiluent is introduced, following its use as a heat-exchange medium and further cooling, to reduce its temperature from 620 F. to a level of F., into a high-pressure separator at a pressure of about 750 p.s.i.g. The normally liquid stream from the cold separator is introduced into a reboiled stripping column for hydrogen sulfide removal and depentanization. The hydrogen sulfide stripping column functions at conditions of temperature and pressure required to concentrate a C to C aromatic stream as a bottoms fraction. With respect to the overall product distribution, only 690 lbs./ hr. of pentanes and lighter hydrocarbons is indicated in the stripper overhead. The aromatic concentrate is recovered in an amount of about 40,070 lbs./ hr. (the fresh feed is 40,120 lbs. /hr.); these results are achieved with a hydrogen consumption of only 660 s.c.f./bbl. With respect to the desired product, the aromatic concentration is 78.0, the sulfur concentration is less than 1.0 p.p.m. by weight, and the diene value is essentially nil.

EXAMPLE II This example is presented to illustrate still another bydrocarbon hydroprocessing scheme for the improvement of the jet fuel characteristics of sulfurous kerosene boiling range fractions. The improvement is especially noticeable in the IPT Smoke Point, the concentration of aromatic hydrocarbons and the concentration of sulfur. A two-stage process wherein desulfurization is eifected in the first reaction zone at relatively mild severities which result in a normally liquid product effluent containing from about 15 to about 35 p.p.m. of sulfur by weight. Aromatic saturation is the principal reaction effected in the second reaction zone, having disposed therein a catalytic composite of alumina, a halogen com ponent, a Group VIII noble metal component and a germanium component.

Suitable charge stocks are kerosene fractions having an initial boiling point as low as about 300 F., and an end boiling point as high as about 575 F., and, in some instances, up to 600 F. Exemplary of such kerosene fractions are those boiling from about 300 F. to about 550 F., from 330 F. to about 500 F., from 330 F. to about 530 F., etc. As a specific example, a kerosene obtained from hydrocracking a Mid-continent slurry oil, having a gravity of about 30.5 API, an initial boiling point of about 388 R, an end boiling point of about 522 F., has an IPT Smoke Point of 17.1 mm., and contains 530 p.p.m. of sulfur and 24.8% by volume of aromatic hydrocarbons. Through the use of the catalytic process of the present invention, the improvement in the jet fuel quality of such a kerosene fraction is most significant with respect to raising the IPT Smoke Point, and reducing the concentration of sulfur and the quantity of aromatic hydrocarbons. Specifications regarding the poorest quality of jet fuel, commonly referred to as Jet-A, Jet-Al and Jet-B call for a sulfur concentration of about 0.3% by weight maximum (3,000 p.p.m.), a minimum IPT Smoke Point of 25 mm. and a maximum aromatic concentration of about 20.0 vol. percent.

The charge stock is admixed with recycled hydrogen in an amount within the range of from about 1,000 to about 2,000 s.c.f./bb1. This mixture is heated to a temperature level necessary to control the maximum catalyst bed temperature below about 750 F., and preferably not above 700 F with a lower catalyst bed temperature of about 600 F. The catalyst, a well known standard desulfurization catalyst containing about 2.2% by weight of cobalt and about 5.7% by Weight of molybdenum, composited with alumina is disposed in a reaction zone maintained under an imposed pressure in the range of from about 500 to about 1,100 p.s.i.g. The LHSV is in the range of about 0.5 to about 10.0, and preferably from about 0.5 to about 5.0. The total product effiuent from this first catalytic reaction zone is separated to provide a hydrogen-rich gaseous phase and a normally liquid hydrocarbon stream containing 15 p.p.m. to about 35 p.p.m. of sulfur by weight. The normally liquid phase portion of the first reaction zone efiiuent is utilized as the fresh feed charge stock to the second reaction zone. In this particular instance, the first reaction zone decreases the sulfur concentration to about 25 p.p.m., the aromatic concentration to about 16.3% by volume, and has increased the IPT Smoke Point to a level of about 21.5 mm.

The catalytic composite within the second reaction zone comprises alumina, 0.375% by weight of platinum, 0.30% by weight of germanium and about 0.60% by weight of combined chloride, calculated on the basis of the elements. The reaction zone is maintained at a pressure of about 400 to about 1,500 p.s.i.g. and the hydrogen circulation rate is in the range of 1,500 to about 10,000 s.c.f./bbl. The LHSV, hereinbefore defined, is in the range of from about 0.5 to about 5.0, and preferably from about 0.5 to about 3.0. It is preferred to limit the catalyst bed temperature in the second reaction zone to a maximum level of about 750 F. With a catalyst of this particular chemical and physical characteristics, optimum aromatic saturation, processing a feed stock containing from about 15 to about 35 p.p.m. of sulfur, is effected at maximum catalyst bed temperatures in the range of about 625 F. to about 750 F. With respect to the normally liquid kerosene fraction, recovered from the condensed liquid removed from the total product eflluent, the sulfur concentration is effectively nil, being about 0.1 p.p.m. The quantity of aromatic hydrocarbons has been decreased to a level of about 0.75% by volume and the IPT Smoke Point has been increased to about 36.3 mm.

With respect to another kerosene fraction, having an IPT Smoke Point of about 20.5 mm., an aromatic concentration of about 19.3 vol. percent and a sulfur concentration of about 17 p.p.m. by weight, the same is processed in a catalytic reaction zone at a pressure of about 850 p-.s.i.g. and a maximum catalyst bed temperature of about 725 F. The LHSV is about 1.35, and the hydrogen circulation rate is about 8,000 s.c.f./bbl. The catalytic composite disposed within the reaction zone comprises alumina, 0.25% by weight of platinum, 0.40% by weight of germanium, about 0.35% by weight of combined chloride and 0.35% by weight of combined fluoride. Following separation and distillation, to concentrate the kerosene fraction, analyses indicate that the Smoke Point has been increased to a level of about 36.9 mm., the aromatic concentration has been lowered to about 0.6% by volume and the sulfur concentration is essentially nil.

The foregoing specification, and particularly the examples, indicates the method by which the present invention is effected, and the benefits afforded through the utilization thereof.

What is claimed is:

1. A process for hydrotreating a hydrocarbon distillate containing conjugated di-olefinic hydrocarbons which comprises reacting said distillate with hydroen at a temperature of from about 200 F. to about 500 F., a pressure of from about 400 to about 1000 p.s.i.g., a liquid hourly space velocity of from about 0.5 to about 10.0 and a hydrogen concentration of from about 1000 to about 10000 s.c.f./bbl. in contact with a catalytic composite of a porous carrier material with from 0.01% to about 2.0% by Weight of a Group VIII noble metal component, from 0.01% to about 5.0% by weight of a germanium component and from about 0.01% to about 1.5% by weight of an alkalinous metal component, on an elemental basis, and recovering a hydrotreated distillate substantially free of conjuated di-olefinic hydrocarbons.

2. The process of claim 1 further characterized in that the metal of said Group VIII comonent is platinum.

3. The process of claim 1 further characterized in that said carrier material is alumina.

References Cited UNITED STATES PATENTS 2,784,147 3/ 1957 Strecker et a1. 252463 2,861,959 11/1958 Thorn et al. 208138 2,906,700 9/1959 Stine et a1. 208-138 2,906,701 9/ 1959 Stine et ai. 208-138 3,098,030 7/ 1963 Coonradt et a1 208111 3,116,233 12/1963 Douwes et al. 208-255 DANIEL E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R. 

